CA2005967C - Highly effective polarizers - Google Patents
Highly effective polarizersInfo
- Publication number
- CA2005967C CA2005967C CA 2005967 CA2005967A CA2005967C CA 2005967 C CA2005967 C CA 2005967C CA 2005967 CA2005967 CA 2005967 CA 2005967 A CA2005967 A CA 2005967A CA 2005967 C CA2005967 C CA 2005967C
- Authority
- CA
- Canada
- Prior art keywords
- compound
- nickel
- polarizers
- polymerization
- films
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 13
- 229920001197 polyacetylene Polymers 0.000 claims abstract description 13
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000008033 biological extinction Effects 0.000 claims abstract description 10
- 230000010287 polarization Effects 0.000 claims abstract description 8
- 230000000903 blocking effect Effects 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000010410 layer Substances 0.000 claims description 18
- -1 nickel (0) compound Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000012790 adhesive layer Substances 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims 2
- 150000002431 hydrogen Chemical group 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 11
- 239000012792 core layer Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- MZRSAJZDYIISJW-UHFFFAOYSA-N 1-phenyl-2-(triphenyl-$l^{5}-phosphanylidene)ethanone Chemical compound C=1C=CC=CC=1C(=O)C=P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 MZRSAJZDYIISJW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 206010038776 Retching Diseases 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000091 aluminium hydride Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- HOMQMIYUSVQSHM-UHFFFAOYSA-N cycloocta-1,3-diene;nickel Chemical compound [Ni].C1CCC=CC=CC1.C1CCC=CC=CC1 HOMQMIYUSVQSHM-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- ZBGRMWIREQJHPK-UHFFFAOYSA-N ethenyl 2,2,2-trifluoroacetate Chemical group FC(F)(F)C(=O)OC=C ZBGRMWIREQJHPK-UHFFFAOYSA-N 0.000 description 1
- BMGYATBBKQVAAI-UHFFFAOYSA-N ethenyl acetate;2,2,2-trifluoroacetic acid Chemical compound CC(=O)OC=C.OC(=O)C(F)(F)F BMGYATBBKQVAAI-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 230000002226 simultaneous effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/91—Product with molecular orientation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Abstract
Highly effective polarizers are described having a degree of polarization P of at least 95% and a dichroic ratio Q E
= quotient of the extinction in the blocking position to the extinction in the transmitting position, of 10 or more over almost the whole wavelength range of visible light between 400 and 800 nm, the said polarizers comprising polymer products containing polyacetylene, in whose matrix 70 to 90% of all comonomer units are vinyl alcohol units. The polarizers are used in the form of films with a stretch ratio (see fig. I) (1 = length after stretching, l o = length before stretching) of more than 300%. They can be produced by polymerization of acetylene in the solution of a copolymer in which 70 to 90% of all comonomer units are vinyl alcohol units, in the presence of a nickel catalyst.
= quotient of the extinction in the blocking position to the extinction in the transmitting position, of 10 or more over almost the whole wavelength range of visible light between 400 and 800 nm, the said polarizers comprising polymer products containing polyacetylene, in whose matrix 70 to 90% of all comonomer units are vinyl alcohol units. The polarizers are used in the form of films with a stretch ratio (see fig. I) (1 = length after stretching, l o = length before stretching) of more than 300%. They can be produced by polymerization of acetylene in the solution of a copolymer in which 70 to 90% of all comonomer units are vinyl alcohol units, in the presence of a nickel catalyst.
Description
~0~S967 Highly effective polarizers The invention relates to highly effective polari-zers made from polymer products cont~in;ng polyacetylene, whose matrix is a copolymer in which 70 to 90~ o~ all comonomer units are vinyl alcohol units, the s~id polari-zers havin~ a hiqh dichroic ratio Q~ with a simultaneou~lyvery high degree of polarization P. Polarizers o~ this type are used as film.
The production of polarizing films based on polyvinyl alcohol and iodine is disclosed for example in DD 210/342. In this instance, a polyvinyl alcohol film is subsequently coloured. In order to obtain results which are in any way satisfactory, a complicated production and post~treatmen~ process is necessary. Nevertheless, as a rule only a portion of the film obtained in this manner is usable~ In practice, the produc~ion of polarizing films of this type i~ limited to iodine and additionally only a few substances with highly effective dichroic behaviour, which limits the applicability of the said films.
Furthe -re, EP 249,019 discIosës improved polarizers based on polyacetylene bonded to polymer matrices. The films obtained therefrom already exhibit a good optical quality. ~hus, for example, after the polymeri~ation of acetyiene in a solution of polyvinyl alcohol in DMF, a polari~ing film is obtained which has a light polarizing effec~ of more than 90% after 4-fold stretching.
Howe~er, these films disclosed in the EP patent Le A ~6 406 -Foreign countri~s , :
, . , ~ . .
20(~59~7 application mentioned still do not have a dichroic ratio which is sufficiently high for ~high tech" applications, this ratio being defined as the quotient QE Of the extinc-tion in the blocking position to the extinc-tion in the transmitting position. The film mentioned in -the ex-emplary embodiment of the EP patent application mentioned is xeddish-brown coloured.
Highly effective polarizers in the form of stretched films have now been found, made from polymer products cont~ining polyacetylene, whose matrix is a copolymer in which 70 to 90% of all comonomer units are vinyl alcohol unitsr ~he said polarizers having a m~i degree of polarization P of at least 95% and a dichroic ratio QEI where Q~ = quotient of the extinction in the blocking position to the extinction in the transmitting position = 10 or more over almost the whole wavelength range of visible light ~rom 400 to 800 nm.
The polarizing effect continues in the near IR
and W region.
Polarizers of this type are used as films in ~hich ~ preferrecl directivn is pro~uced uy s_retching. l;
has furthermore been found that the high effectiveness of the polarizers according to the invention can be Lmproved at relatively high stretch ratios. The polariz~rs accord-ing to the invention have a stretch ratio 6 of more than 300%, preferably at least 500~, particularly preferably at least 600%. Here, the stretch ratio 6 iS defined by the quotient Le A 26 406 - 2 -, ~ 1. ' ' , ~0~3S~67 1--lo = ~ 100 lo in which l is the length after stretching and lo is the length before stretching.
In addition to the dichroic ratio Q~ = 10 or more, the high~y effective polarizers accordin~ to the inven-tion additionally have a high ~irllm degree of polari-zation P of at least 95~, preferably at least 98%, parti-cularly preferably at least 99%. The ~iml~ values Of QE
attain values of 15 and above, preferably 20 and above.
Here, the degree of polarization P is given by the relationship between the transmission of linearly polarized light in the transmitting position and the blocking position respectively (Transmiss. Trans and Transmiss. BLock respectively):
Transmiss. trans. - Tr~n~ri SS . block - Transmiss. trans. ~ Transmiss. block The dichroic ratio QE is defined as the quotient ; of the extinction in the blocking position to the extinc-tion in the transmitting position. This ratio applies to a certain wavelength and is limited in the case of suitable dichroic dyes to a narrow wavelength range of visible light. This is discernible from the inherent colour of polarizers produced with the aid o~ dichroic dyes; moreover, the materials mentioned are difficult to distribute uniformly over a relatively large surface of Le A 26 406 - 3 -~35967 a fîlm which is to be coloured with the materi-als.
On the other hand, the polarizers according to the invention exhibit a high Q~ value over almost the whole range of visible light and are therefore~substan-tially colour-neutral, which is discernible from their inherent grey colour. This corresponds to the de~ire to have available colour-neutral polarizers with a high l ght/dar~ contrast. Thi~ i~ importan~ fo~ o~ c~l C~~ n; cation devices, such as LCDs with externally or internally located polarizing film, in which high resolu-tion and good legibility are desired.
The highIy effective polarizers according to the invention may be produced by polymerization of acetylene in the solution of a copolymer in which 70 to 90% of all comonomer units are vinyl alcohol units, in the presence of a nickel catalyst which is obtained by reacting a nickel (0) compound or a compound which can be converted in situ into a nickel (0) compound, with phosphorus compounds of the formulae R3' R6 ~7 R2-P=CH-R4 (I) (I) and R5-P=C (II) Phenyl CO-Phenyl in which R1, R2 and R3 independently of each other denote Cl-C8-alkyl, phenyl or benzyl, R4 represents hydrogen, C1-C8-alkyl or phenyl and R5r R6 and R7 independently of each other denote Cl-C8-alkyl or phenyl, and R7 may additionally denote hydrogen or acyl, Le A 26 406 - 4 -~S~7 or in the presence of nickel catalysts which can be produced by reacting a nickel (0) compound or a compound which can be converted in situ into a nicXel (0) com-- pound, with an adduct or a mixture of p-benzoquinone and a phosphine of the formula ~ (III) Phenyl in which R5 and R6 have the given -~n; ng, and with a compound of the formula (I ? .
These polymers are processed into films, which are stretched.
Preferably, the acetylene polymerization is carried ou~ in the presence of nickel catalysts which can he prepared by reacting a nickel (0) compound or a compound which can be converted in situ into a nickel (0) compound, with compounds of the formulae ~ ,R
R2 - P=CH-Phenyl (IV) and (Phenyl)3P C~c ph~ny!tv) Rl .
in which Rl, R2, R3 and R7 have the meaning given above, or in the presence of nickel catalysts which can be prepared by reacting a nickel ~0) compound or a compound which can be converted in situ into a nickel (0) compound, with an adduct or mixture of p-benzo~uinone and ~riphenylphos-phine and with a compound of the formula ~IV).
Le A 26 406 - 5 -. ~
- .
~ .
:. . . .
. ~ ~ .. . ~ . .
6~
In order to prepare the catalyst 1-4 mol of the compound of the formula (I) or (IV) and 1-4 mol of the compound of the formula (II) or (V), are used per mol of nickel (0) compound, and preferably about 1 mol o~ the compound of the formula (I) or (IV) and about 1 mol of the compound of the formula (II) or (V) are used per mol of the nickel (0) compound. Identical ratios are applied-, if a p-benzoquinone/phosphine adduct ox a p-benzoquinone/
phosphine mixture of the type described replaces a compound o~ the formula (II) or (V).
The temperature for preparing the catalyst is 0 to 100~C, preferably 20 to 70~C. The preparation is carried out with the exclusion of oxygen, preferably in a solvent, which must be inert towards the reactants, such as benzene, toluene, cyclohe~Ane or n-hexane. After being prepared, the catalyst is normally isolated as a solid by filtration, the solution being concentrated and/or cooled beforehand as required. The catalyst may however also be used directly for the polymerization of acetylene without being isolated i.e. as a solution.
Examples of nickel (0) compounds which may b~
mentioned are Ni(cyclooctadiene) 2 and Ni(allyl) 2 - The following may be mentioned by way of example as nickel compounds which can be converted in situ into nickel (0) compounds: Ni acetylacetonate, Ni octanoate and Ni stearate, which can be reduced with the aid of customary reducing agents, such as borohydride, aluminium hydride, aluminium alkyls or organolithium compounds.
The following may be mentioned as examples of C1-C~-alkyl, which may be straight-chain or branched: methyl, Le A 26 406 - 6 -!
~:Q~67 ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the isomeric amyls, hexyls and octyls. A preferred alkyl has 1 4 carbon atoms.
As acyl, C1-CB-alkylcarbonyl or phenylcarbonyl may be mentioned, such as acetyl, propionyl, butyryl, C5-alkyl-carbonyl, C8-alkyl-carbonyl, benzoyl or substituted benzoy~. A preferred acyl is substituted or unsubstitu~
Cl-C4-alkylcarbonyl or benzoyl. Acetyl and benzoyl are particularly preferred~
Alkyl, phenyl and benzyl may be mono- to trisub-stituted, preferably mono or disubstituted, particularly preferably monosubstituted by Cl-C4-alkyl, by Cl-C4-alkoxyl by phenyl or phenoxy, and in the case of multiple sub-stitution, the substituents may be taken variously from the given list.
The amount of nickel catalyst used for the acetylene polymerization is not critical. Typical cata-lyst concentrations are 10~l to 10-5, preferably 10-2-10-4 mol, particularly preferably 1 x 10-3 to 5 x 10-3 mol of nickel catalyst per litre of polymerization mixture.
The polymerization of the ace~ylene may be carried out both continuously and discontinuo'usly~ Here, a temperature of 20-120~C, preferably 40 to 110~C, par-ticularly preferably 50-90~C is maintained.
The polymerization can be carried out at normal pressure, but it is also possible to polym~ri2e under increased pressure, for example at 1.01 to 20 bar, optionally as a mixture with an inert gas, such as Nz. The acetylene can be taken from a pressure bottle and used without further purification. In the case of catalysts Le A 26 406 - 7 -. ~
which are sensitive to acetone it may be necessary to freeze out beforehand any asetone contained in the acetylene in a cold trap.
The acetylene polymerization is carried out in the solution of a copolymer in which 70 to 90% o~ all comonomer units are vinyl alcohol units and which ma~ be present in a pre~Q~in~ntly tactic or atactic fo~m. The r~;ning 30 to 10% of all comonomer units may for example be ethylene units and/or vinyl acetate units and/or vinyl trifluoroacetate units and/or units of other copolymerizable olefinic monomers. The preparation of copolymers of this type is known to those skilled in the art and can for example be carried out in such a way that an ethylene-vinyl acetate (trifluoroacetate) copolymer or a vinyl acetate (trifluoroacetate) homopolymer or another suitable copolymer, which contains monomer units which are convertible into vinyl alcohol units, is saponified or converted up to the given content of free vinyl alcohol units.
Examples of solvents for ~he polymerization are dimethylformamide (DMF), dimethyl sulphoxide (DMSO), dimethylacetamide and so on. The concentration of the polymer in the solvent is 1-20% by weight, preferably 2-10~ ~y weight.
The polymerization medium (soluticn of the copolymer) may contain water in the percenta~e range 0.001 to 5~ by weight, for example, without the catalyst being deactivated. Water of this type may be introduced via the solvent, via the copolymer or via both solvent and copolymer. The H2O content is preferably however as Le A 26 406 - 8 -j,:
: . .:. ,:: :~ .; :
, Q~at0S9~
low as possible and particularly preferably approaches the value zero.
In order to produce the highly effective polari-zers according to the invention the polymerization of acetylene is carried out in a period of 5-1000 ~ec., preferably 5-600 sec. A particular advantaye lies in the possibility of carrying out the reaction in a very short time, ~or example in 5-300 sec., preferably 5-200 sec.
Such very short times are for example to be used when a very thin layer of the polymer solu~ion cont~;n;ng the catalyst is treated with the acetylene~
The solutions of polymer products cont~i n; ng polyacetylene which can be obtained in this manner exhibit a blue colour, which is also retained in the solid polymer product cont~ining polyacetylene after evaporation of the solvent. It is surprising that the blue colour provides a simply recognizable external indication of the high effectiveness of the polarizers according to the invention.
The properties of the polymer products cont~;n;ng polyacetylene are consistent with a structurai model, in which'lateral branches of'''polyacetylene are'g'ra~ted onto the polymer matrix.
The polarizers according to the invention are produced in the form of films by casting or extrusion, and these films are subsequently stretched. For casting, the polymerization solution can be used directly in a manner known to those skilled in the art. For this purpose, polymer solutions cont~i n i ng polyacetylene may also be blended with initial polymer solu~ions not Le A 26 406 - 9 -~ : .. ~: .
.:
- .
.
'7 containing any polyacetylene or with other polymer solutions cont~ining polyacetylene.
Depending on polymeri~ation parameters such as tLme, temperature, catalyst composition and 50 on, particularly however on the catalyst composition, the ~sxi QE values mentioned above can occur in different ranges of visible light. It may be desirable to wic1en the range of the m~i Q~ value by using more than one catalyst for the polymerization and thus producing several QE m~ . An identical effect is achieved in principle by blending polymer solutions or precipitated polymers which have been prepared using different poly-merization parameters.
The polarizing film may also be obtained however, by stretching a coagulated film. In this case, after the casting process the solvent is not removed by evaporation (at room temperature or elevated temperature and/or reduced pressure) but is 1~ ved by contact with a precipitating agent into which the solvent of the poly-merization (casting) solution diffuses, only the gener-ally more readily volatile precipitating agent having subsequently to be evaporated.
Examples of precipitating agents are toluene, cyclohe~n~, acetone, methanol, ethanol and others, in which partially saponified PVAC is not soluble.
However, the polymer product cont~;n;ng poly-acetylene may also be precipitated from the polymeriz-ation solution with one of the precipitating agents mentioned and isolated as a solid in the customary ~snn~r.
Le A 26 406 10 -~: : : : .
~ S~67 The solid polymer product cont~in;ng polyacetyl-ene is again soluble in one of the solvents mentioned for the pol~merization or in water and can be cast into films from a solution of this type. It may be desirable to add a plasticizer known to those skilled in the art to the casting solution. Examples of customary and suitable plasticizers which may be used are ~lycerol or ethylene glycol in customary amounts, such as about 1-50%, rela-ti~e to the polymer. Additives of this kind are par-ticularly advantageous when the polymer product contain-ing polyacetylene which has been precipi~ated is pro-cessed ~rom an aqueous casting solution.
The polarizers according to the invention may he processed into laminates by applying adhesive layers and covering layers on one or both sides and are protected in this form from mechanical and chemical damage. The degree of order of a stretched polari~ing film is not disturbed by the l~m; n~tion process. The invention therefore relates also to this particular embodiment of the polari-zers described.
While in the case of many laminates, mechdnicalproperties such as strength, energy absorption charac-teristics (safety glasses) and generally an adequate adhesion of the laminate components is of prime ~oncern/
in the case of the lamination of the highly effective polarizers according to the invention there are addition-ally other requirements, namely 1) a high light transparency, whereby all clouding phenomena must be excluded, 2) a high degree of light fastness Le A 26 406 ~ ~.
. . ~
. : . ~ .. :
~Ot~S96~7 3~ protection of the polarizing core layer from chemical influences from the environment and 4) compatibility of the adhesive layers and option-ally of the outer layers with the polarizing core layer without imp~;rme~t of the optical properties.
Examples of suitable outer layers are aromatic polyesters, polyacrylonitriles, poly(meth)acrylates, polysulphones, aromatic polycarbonates, cellulose ace-tates, cellulose acetate butyrates, polyamides, polyhy-dantoins, polyimides, polyamidimides, polyparaphenylene-benzo bisimidazoles and -oxazoles, polyether ketones and mineral glasses, where in particular the polyesters, polyacrylates, polycarbonates, cellulose esters and mineral glasses may be mentioned. The transparency of these materials is their most important feature. They are generally used as thin sheets or as films.
Suitable adhesive layers are thin layers of adhesive materials which do not impair the optical properties of the total laminate which are suitable for bonding the core layer and the outPr layers with adequate adhesive strength and which furthe ~re caus~ no un-desired change in the outër layers and in the polarizing core layer, particularly in the polarizing core layer.
Solvent-free systems or solvent-containing systems are suitable for this purpose. The requirement that no chemical changes within the outer layers and within the polari~ing core layer should be caused, is particularly important in the case of solvent-cont~; n i ng systems.
The following may be mentioned as adhesive materials of this type which are known in principle to Le A 26 406 - 12 -~0~967 those skilled in the art: epoxy resins which are cured with amines, acid anhydrides or polyamides; acrylate systems, which may be monomeric and oligomeric systems with vinyl groups, which may be cured thermally, photo-chemically or by free-radicals after the applicakion of the outer layer; mixtures of polyacrylates with phenolic resins, which are applied in solution; isocyanat~ ~dhe-sives and polyurethanes.
The adhesi~e materials which are to be used as adhesive layers may for example be applied by pouring a solution of this adhesive material onto the polarizing core layer and e~aporating the solvent. The polarizing core layer which has been thus provided on one or both sides with adhesive layers can then be bonded with the outer layers.
It is likewise possible to carry out the proce-dure the other way round by which adhesive matarial is initially applied to the outer layer(s), after which joining of the outer layers, provided with adhesive coats, to the polarizing core layer, is carried out. The thickness of the individual layers may be adjusted within extraordinarily wide lLmits and is not critical to the invention. Thicknesses which may be mentioned are ~rom 0.5 to 50 ~m, preferably 0.5 to 20 ~m, for the adhesive layers and thicknesses of 5 ~m to 1 mm, pref~rably 5 to 100 ~m, for the outer layers. Where outer layers are concerned, however, these may be optical lenses or prisms with greater thicknesses. The core layer may be 1 to 100 ~m, preferably 5 to 50 ~m thick.
The polarizing film according to the invention Le A 26 406 - 13 -20~5~t~7 and also the adhesive layers or outer layers may further-more be stabilized with stabilizers known to those skilled in the art, such as W -absorbers, HALS types and radical interceptors against W radiation, chemical or heat degradation; typical stabilizers for this purpose which may be mentioned are Ionol~ and Bayer W 340~, which however may be supplemented or replacad ~y many o~her stabilizers. No reduction of the optical quality o~ the polarizing film occurs when this is done.
Example 1 Preparation of catalyst 5 mmol of bis-cyclooctadiene-nickel (0) in 100 ml of toluene saturated with dry nitrogen were mixed under nitrogen with 5 mmol of benzoylmethylene-triphenylphos-phorane and 5 mmol of methylene-trimethylphosphoraneO The mixture was heated with vigorous stirring for about 1 hour at 40-60~C. The dark yellowish~brown solution was filtered and concentrated to dryness in vacuo. The yellow catalyst was dissolved in 25 ml of dry dimethylformamide saturated with nitrogen. This solution or a portion thereof was used in the subsequent polymeri~tion of acetylene.
ExamPle 2 Polyvinyl alcohol-polyacet~lene ~PVA-PAC) 5 g of polyvinyl alcohol (PVA; degree of saponi-fication of the polyvinyl acetate 88%) were dissolved under inert gas in 245 g of dry DMF (degassed, N2-satura-ted) at 1~0~C in a 250 ml reaction flask (gas feed, dropping funnel without pressure compensation with N2-feed, stirrer, internal t,he eter, reflux condenser Le A 26 406 - 14 -2~)59~7 with bubble gauge), and then brought to a temperature of 80~C. 1.0 mmol of the catalyst described above was then admixed with stirring to 5 ml of DMF under N2 and a uniform stream of acetylene gas (dry ice/acetone) was introduced for 15 sec. The reaction solution was then filtered through a polyamide cloth having a mesh width of 200 ~m.
The clear blue PVA-PAC solution (absorption ~;mll~ 633 nm) was applied hot with a doctor blade to a PET film as a 400 ~m layer. After evaporation of the sol~ent, a clear, dark blue film was obt~ine~, which was pulled off the base and stretched at a~out 130~C to e =
76~%.
The stretched, transparent, light grey film had - 15 a degree of polarization of 99.4% at 600 nm.
QE - 26.3 QE 2 20 at 580 - 730 nm QE 2 10 at 440 - 780 nm P 2 95~ at 460 - 700 nm.
Examples 3-5 Other catalysts were prepared analogously to Example 1. Their ligands~~~the polymeri~ation conditions and the properties of the polarizing films ob~ained are shown in the following table.
Le A 26 406 - 15 -- ~ . :
:, : ~ -: - . , Z~305916t7 a~
.C ~~
,, ~r O O O
'H O ~ t.) P E-l o O S
o ~ ~ I ~r1 u~
a _, O
O
O O O O .
~ 3'~ a ~ . ~4 O O O
u~ ., ., ., ~
~ P~ v ~ u a ,~
~U C~ Z ~ Z _ Z _, a ..
G
~ ,~ Il O
~ Z
Le A 26 406 - 16 -.
t~ Table: Examples 3-5, Production and propertie~ of polarizing films - ~, r ,le1st absul~Lion St~etch ratio Qe 2 10 t;~ max P ~ 9596 P~
,p No. ~ of the in the wav~ ; in ~he wave reactn. soln. length rar~ge len~th range % ~n mn %
. - , 3 602 732 440-750 19.0 350-700 99.7 . .
: : 4 625 746 500-800 19.9 350-700 99.8 i~'3 637 7~ 450-75~ 25.4 400-700 99.8 .- -... --- : .
- - . . .
,. ~
.
.
= .
~, ~ .
The production of polarizing films based on polyvinyl alcohol and iodine is disclosed for example in DD 210/342. In this instance, a polyvinyl alcohol film is subsequently coloured. In order to obtain results which are in any way satisfactory, a complicated production and post~treatmen~ process is necessary. Nevertheless, as a rule only a portion of the film obtained in this manner is usable~ In practice, the produc~ion of polarizing films of this type i~ limited to iodine and additionally only a few substances with highly effective dichroic behaviour, which limits the applicability of the said films.
Furthe -re, EP 249,019 discIosës improved polarizers based on polyacetylene bonded to polymer matrices. The films obtained therefrom already exhibit a good optical quality. ~hus, for example, after the polymeri~ation of acetyiene in a solution of polyvinyl alcohol in DMF, a polari~ing film is obtained which has a light polarizing effec~ of more than 90% after 4-fold stretching.
Howe~er, these films disclosed in the EP patent Le A ~6 406 -Foreign countri~s , :
, . , ~ . .
20(~59~7 application mentioned still do not have a dichroic ratio which is sufficiently high for ~high tech" applications, this ratio being defined as the quotient QE Of the extinc-tion in the blocking position to the extinc-tion in the transmitting position. The film mentioned in -the ex-emplary embodiment of the EP patent application mentioned is xeddish-brown coloured.
Highly effective polarizers in the form of stretched films have now been found, made from polymer products cont~ining polyacetylene, whose matrix is a copolymer in which 70 to 90% of all comonomer units are vinyl alcohol unitsr ~he said polarizers having a m~i degree of polarization P of at least 95% and a dichroic ratio QEI where Q~ = quotient of the extinction in the blocking position to the extinction in the transmitting position = 10 or more over almost the whole wavelength range of visible light ~rom 400 to 800 nm.
The polarizing effect continues in the near IR
and W region.
Polarizers of this type are used as films in ~hich ~ preferrecl directivn is pro~uced uy s_retching. l;
has furthermore been found that the high effectiveness of the polarizers according to the invention can be Lmproved at relatively high stretch ratios. The polariz~rs accord-ing to the invention have a stretch ratio 6 of more than 300%, preferably at least 500~, particularly preferably at least 600%. Here, the stretch ratio 6 iS defined by the quotient Le A 26 406 - 2 -, ~ 1. ' ' , ~0~3S~67 1--lo = ~ 100 lo in which l is the length after stretching and lo is the length before stretching.
In addition to the dichroic ratio Q~ = 10 or more, the high~y effective polarizers accordin~ to the inven-tion additionally have a high ~irllm degree of polari-zation P of at least 95~, preferably at least 98%, parti-cularly preferably at least 99%. The ~iml~ values Of QE
attain values of 15 and above, preferably 20 and above.
Here, the degree of polarization P is given by the relationship between the transmission of linearly polarized light in the transmitting position and the blocking position respectively (Transmiss. Trans and Transmiss. BLock respectively):
Transmiss. trans. - Tr~n~ri SS . block - Transmiss. trans. ~ Transmiss. block The dichroic ratio QE is defined as the quotient ; of the extinction in the blocking position to the extinc-tion in the transmitting position. This ratio applies to a certain wavelength and is limited in the case of suitable dichroic dyes to a narrow wavelength range of visible light. This is discernible from the inherent colour of polarizers produced with the aid o~ dichroic dyes; moreover, the materials mentioned are difficult to distribute uniformly over a relatively large surface of Le A 26 406 - 3 -~35967 a fîlm which is to be coloured with the materi-als.
On the other hand, the polarizers according to the invention exhibit a high Q~ value over almost the whole range of visible light and are therefore~substan-tially colour-neutral, which is discernible from their inherent grey colour. This corresponds to the de~ire to have available colour-neutral polarizers with a high l ght/dar~ contrast. Thi~ i~ importan~ fo~ o~ c~l C~~ n; cation devices, such as LCDs with externally or internally located polarizing film, in which high resolu-tion and good legibility are desired.
The highIy effective polarizers according to the invention may be produced by polymerization of acetylene in the solution of a copolymer in which 70 to 90% of all comonomer units are vinyl alcohol units, in the presence of a nickel catalyst which is obtained by reacting a nickel (0) compound or a compound which can be converted in situ into a nickel (0) compound, with phosphorus compounds of the formulae R3' R6 ~7 R2-P=CH-R4 (I) (I) and R5-P=C (II) Phenyl CO-Phenyl in which R1, R2 and R3 independently of each other denote Cl-C8-alkyl, phenyl or benzyl, R4 represents hydrogen, C1-C8-alkyl or phenyl and R5r R6 and R7 independently of each other denote Cl-C8-alkyl or phenyl, and R7 may additionally denote hydrogen or acyl, Le A 26 406 - 4 -~S~7 or in the presence of nickel catalysts which can be produced by reacting a nickel (0) compound or a compound which can be converted in situ into a nicXel (0) com-- pound, with an adduct or a mixture of p-benzoquinone and a phosphine of the formula ~ (III) Phenyl in which R5 and R6 have the given -~n; ng, and with a compound of the formula (I ? .
These polymers are processed into films, which are stretched.
Preferably, the acetylene polymerization is carried ou~ in the presence of nickel catalysts which can he prepared by reacting a nickel (0) compound or a compound which can be converted in situ into a nickel (0) compound, with compounds of the formulae ~ ,R
R2 - P=CH-Phenyl (IV) and (Phenyl)3P C~c ph~ny!tv) Rl .
in which Rl, R2, R3 and R7 have the meaning given above, or in the presence of nickel catalysts which can be prepared by reacting a nickel ~0) compound or a compound which can be converted in situ into a nickel (0) compound, with an adduct or mixture of p-benzo~uinone and ~riphenylphos-phine and with a compound of the formula ~IV).
Le A 26 406 - 5 -. ~
- .
~ .
:. . . .
. ~ ~ .. . ~ . .
6~
In order to prepare the catalyst 1-4 mol of the compound of the formula (I) or (IV) and 1-4 mol of the compound of the formula (II) or (V), are used per mol of nickel (0) compound, and preferably about 1 mol o~ the compound of the formula (I) or (IV) and about 1 mol of the compound of the formula (II) or (V) are used per mol of the nickel (0) compound. Identical ratios are applied-, if a p-benzoquinone/phosphine adduct ox a p-benzoquinone/
phosphine mixture of the type described replaces a compound o~ the formula (II) or (V).
The temperature for preparing the catalyst is 0 to 100~C, preferably 20 to 70~C. The preparation is carried out with the exclusion of oxygen, preferably in a solvent, which must be inert towards the reactants, such as benzene, toluene, cyclohe~Ane or n-hexane. After being prepared, the catalyst is normally isolated as a solid by filtration, the solution being concentrated and/or cooled beforehand as required. The catalyst may however also be used directly for the polymerization of acetylene without being isolated i.e. as a solution.
Examples of nickel (0) compounds which may b~
mentioned are Ni(cyclooctadiene) 2 and Ni(allyl) 2 - The following may be mentioned by way of example as nickel compounds which can be converted in situ into nickel (0) compounds: Ni acetylacetonate, Ni octanoate and Ni stearate, which can be reduced with the aid of customary reducing agents, such as borohydride, aluminium hydride, aluminium alkyls or organolithium compounds.
The following may be mentioned as examples of C1-C~-alkyl, which may be straight-chain or branched: methyl, Le A 26 406 - 6 -!
~:Q~67 ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the isomeric amyls, hexyls and octyls. A preferred alkyl has 1 4 carbon atoms.
As acyl, C1-CB-alkylcarbonyl or phenylcarbonyl may be mentioned, such as acetyl, propionyl, butyryl, C5-alkyl-carbonyl, C8-alkyl-carbonyl, benzoyl or substituted benzoy~. A preferred acyl is substituted or unsubstitu~
Cl-C4-alkylcarbonyl or benzoyl. Acetyl and benzoyl are particularly preferred~
Alkyl, phenyl and benzyl may be mono- to trisub-stituted, preferably mono or disubstituted, particularly preferably monosubstituted by Cl-C4-alkyl, by Cl-C4-alkoxyl by phenyl or phenoxy, and in the case of multiple sub-stitution, the substituents may be taken variously from the given list.
The amount of nickel catalyst used for the acetylene polymerization is not critical. Typical cata-lyst concentrations are 10~l to 10-5, preferably 10-2-10-4 mol, particularly preferably 1 x 10-3 to 5 x 10-3 mol of nickel catalyst per litre of polymerization mixture.
The polymerization of the ace~ylene may be carried out both continuously and discontinuo'usly~ Here, a temperature of 20-120~C, preferably 40 to 110~C, par-ticularly preferably 50-90~C is maintained.
The polymerization can be carried out at normal pressure, but it is also possible to polym~ri2e under increased pressure, for example at 1.01 to 20 bar, optionally as a mixture with an inert gas, such as Nz. The acetylene can be taken from a pressure bottle and used without further purification. In the case of catalysts Le A 26 406 - 7 -. ~
which are sensitive to acetone it may be necessary to freeze out beforehand any asetone contained in the acetylene in a cold trap.
The acetylene polymerization is carried out in the solution of a copolymer in which 70 to 90% o~ all comonomer units are vinyl alcohol units and which ma~ be present in a pre~Q~in~ntly tactic or atactic fo~m. The r~;ning 30 to 10% of all comonomer units may for example be ethylene units and/or vinyl acetate units and/or vinyl trifluoroacetate units and/or units of other copolymerizable olefinic monomers. The preparation of copolymers of this type is known to those skilled in the art and can for example be carried out in such a way that an ethylene-vinyl acetate (trifluoroacetate) copolymer or a vinyl acetate (trifluoroacetate) homopolymer or another suitable copolymer, which contains monomer units which are convertible into vinyl alcohol units, is saponified or converted up to the given content of free vinyl alcohol units.
Examples of solvents for ~he polymerization are dimethylformamide (DMF), dimethyl sulphoxide (DMSO), dimethylacetamide and so on. The concentration of the polymer in the solvent is 1-20% by weight, preferably 2-10~ ~y weight.
The polymerization medium (soluticn of the copolymer) may contain water in the percenta~e range 0.001 to 5~ by weight, for example, without the catalyst being deactivated. Water of this type may be introduced via the solvent, via the copolymer or via both solvent and copolymer. The H2O content is preferably however as Le A 26 406 - 8 -j,:
: . .:. ,:: :~ .; :
, Q~at0S9~
low as possible and particularly preferably approaches the value zero.
In order to produce the highly effective polari-zers according to the invention the polymerization of acetylene is carried out in a period of 5-1000 ~ec., preferably 5-600 sec. A particular advantaye lies in the possibility of carrying out the reaction in a very short time, ~or example in 5-300 sec., preferably 5-200 sec.
Such very short times are for example to be used when a very thin layer of the polymer solu~ion cont~;n;ng the catalyst is treated with the acetylene~
The solutions of polymer products cont~i n; ng polyacetylene which can be obtained in this manner exhibit a blue colour, which is also retained in the solid polymer product cont~ining polyacetylene after evaporation of the solvent. It is surprising that the blue colour provides a simply recognizable external indication of the high effectiveness of the polarizers according to the invention.
The properties of the polymer products cont~;n;ng polyacetylene are consistent with a structurai model, in which'lateral branches of'''polyacetylene are'g'ra~ted onto the polymer matrix.
The polarizers according to the invention are produced in the form of films by casting or extrusion, and these films are subsequently stretched. For casting, the polymerization solution can be used directly in a manner known to those skilled in the art. For this purpose, polymer solutions cont~i n i ng polyacetylene may also be blended with initial polymer solu~ions not Le A 26 406 - 9 -~ : .. ~: .
.:
- .
.
'7 containing any polyacetylene or with other polymer solutions cont~ining polyacetylene.
Depending on polymeri~ation parameters such as tLme, temperature, catalyst composition and 50 on, particularly however on the catalyst composition, the ~sxi QE values mentioned above can occur in different ranges of visible light. It may be desirable to wic1en the range of the m~i Q~ value by using more than one catalyst for the polymerization and thus producing several QE m~ . An identical effect is achieved in principle by blending polymer solutions or precipitated polymers which have been prepared using different poly-merization parameters.
The polarizing film may also be obtained however, by stretching a coagulated film. In this case, after the casting process the solvent is not removed by evaporation (at room temperature or elevated temperature and/or reduced pressure) but is 1~ ved by contact with a precipitating agent into which the solvent of the poly-merization (casting) solution diffuses, only the gener-ally more readily volatile precipitating agent having subsequently to be evaporated.
Examples of precipitating agents are toluene, cyclohe~n~, acetone, methanol, ethanol and others, in which partially saponified PVAC is not soluble.
However, the polymer product cont~;n;ng poly-acetylene may also be precipitated from the polymeriz-ation solution with one of the precipitating agents mentioned and isolated as a solid in the customary ~snn~r.
Le A 26 406 10 -~: : : : .
~ S~67 The solid polymer product cont~in;ng polyacetyl-ene is again soluble in one of the solvents mentioned for the pol~merization or in water and can be cast into films from a solution of this type. It may be desirable to add a plasticizer known to those skilled in the art to the casting solution. Examples of customary and suitable plasticizers which may be used are ~lycerol or ethylene glycol in customary amounts, such as about 1-50%, rela-ti~e to the polymer. Additives of this kind are par-ticularly advantageous when the polymer product contain-ing polyacetylene which has been precipi~ated is pro-cessed ~rom an aqueous casting solution.
The polarizers according to the invention may he processed into laminates by applying adhesive layers and covering layers on one or both sides and are protected in this form from mechanical and chemical damage. The degree of order of a stretched polari~ing film is not disturbed by the l~m; n~tion process. The invention therefore relates also to this particular embodiment of the polari-zers described.
While in the case of many laminates, mechdnicalproperties such as strength, energy absorption charac-teristics (safety glasses) and generally an adequate adhesion of the laminate components is of prime ~oncern/
in the case of the lamination of the highly effective polarizers according to the invention there are addition-ally other requirements, namely 1) a high light transparency, whereby all clouding phenomena must be excluded, 2) a high degree of light fastness Le A 26 406 ~ ~.
. . ~
. : . ~ .. :
~Ot~S96~7 3~ protection of the polarizing core layer from chemical influences from the environment and 4) compatibility of the adhesive layers and option-ally of the outer layers with the polarizing core layer without imp~;rme~t of the optical properties.
Examples of suitable outer layers are aromatic polyesters, polyacrylonitriles, poly(meth)acrylates, polysulphones, aromatic polycarbonates, cellulose ace-tates, cellulose acetate butyrates, polyamides, polyhy-dantoins, polyimides, polyamidimides, polyparaphenylene-benzo bisimidazoles and -oxazoles, polyether ketones and mineral glasses, where in particular the polyesters, polyacrylates, polycarbonates, cellulose esters and mineral glasses may be mentioned. The transparency of these materials is their most important feature. They are generally used as thin sheets or as films.
Suitable adhesive layers are thin layers of adhesive materials which do not impair the optical properties of the total laminate which are suitable for bonding the core layer and the outPr layers with adequate adhesive strength and which furthe ~re caus~ no un-desired change in the outër layers and in the polarizing core layer, particularly in the polarizing core layer.
Solvent-free systems or solvent-containing systems are suitable for this purpose. The requirement that no chemical changes within the outer layers and within the polari~ing core layer should be caused, is particularly important in the case of solvent-cont~; n i ng systems.
The following may be mentioned as adhesive materials of this type which are known in principle to Le A 26 406 - 12 -~0~967 those skilled in the art: epoxy resins which are cured with amines, acid anhydrides or polyamides; acrylate systems, which may be monomeric and oligomeric systems with vinyl groups, which may be cured thermally, photo-chemically or by free-radicals after the applicakion of the outer layer; mixtures of polyacrylates with phenolic resins, which are applied in solution; isocyanat~ ~dhe-sives and polyurethanes.
The adhesi~e materials which are to be used as adhesive layers may for example be applied by pouring a solution of this adhesive material onto the polarizing core layer and e~aporating the solvent. The polarizing core layer which has been thus provided on one or both sides with adhesive layers can then be bonded with the outer layers.
It is likewise possible to carry out the proce-dure the other way round by which adhesive matarial is initially applied to the outer layer(s), after which joining of the outer layers, provided with adhesive coats, to the polarizing core layer, is carried out. The thickness of the individual layers may be adjusted within extraordinarily wide lLmits and is not critical to the invention. Thicknesses which may be mentioned are ~rom 0.5 to 50 ~m, preferably 0.5 to 20 ~m, for the adhesive layers and thicknesses of 5 ~m to 1 mm, pref~rably 5 to 100 ~m, for the outer layers. Where outer layers are concerned, however, these may be optical lenses or prisms with greater thicknesses. The core layer may be 1 to 100 ~m, preferably 5 to 50 ~m thick.
The polarizing film according to the invention Le A 26 406 - 13 -20~5~t~7 and also the adhesive layers or outer layers may further-more be stabilized with stabilizers known to those skilled in the art, such as W -absorbers, HALS types and radical interceptors against W radiation, chemical or heat degradation; typical stabilizers for this purpose which may be mentioned are Ionol~ and Bayer W 340~, which however may be supplemented or replacad ~y many o~her stabilizers. No reduction of the optical quality o~ the polarizing film occurs when this is done.
Example 1 Preparation of catalyst 5 mmol of bis-cyclooctadiene-nickel (0) in 100 ml of toluene saturated with dry nitrogen were mixed under nitrogen with 5 mmol of benzoylmethylene-triphenylphos-phorane and 5 mmol of methylene-trimethylphosphoraneO The mixture was heated with vigorous stirring for about 1 hour at 40-60~C. The dark yellowish~brown solution was filtered and concentrated to dryness in vacuo. The yellow catalyst was dissolved in 25 ml of dry dimethylformamide saturated with nitrogen. This solution or a portion thereof was used in the subsequent polymeri~tion of acetylene.
ExamPle 2 Polyvinyl alcohol-polyacet~lene ~PVA-PAC) 5 g of polyvinyl alcohol (PVA; degree of saponi-fication of the polyvinyl acetate 88%) were dissolved under inert gas in 245 g of dry DMF (degassed, N2-satura-ted) at 1~0~C in a 250 ml reaction flask (gas feed, dropping funnel without pressure compensation with N2-feed, stirrer, internal t,he eter, reflux condenser Le A 26 406 - 14 -2~)59~7 with bubble gauge), and then brought to a temperature of 80~C. 1.0 mmol of the catalyst described above was then admixed with stirring to 5 ml of DMF under N2 and a uniform stream of acetylene gas (dry ice/acetone) was introduced for 15 sec. The reaction solution was then filtered through a polyamide cloth having a mesh width of 200 ~m.
The clear blue PVA-PAC solution (absorption ~;mll~ 633 nm) was applied hot with a doctor blade to a PET film as a 400 ~m layer. After evaporation of the sol~ent, a clear, dark blue film was obt~ine~, which was pulled off the base and stretched at a~out 130~C to e =
76~%.
The stretched, transparent, light grey film had - 15 a degree of polarization of 99.4% at 600 nm.
QE - 26.3 QE 2 20 at 580 - 730 nm QE 2 10 at 440 - 780 nm P 2 95~ at 460 - 700 nm.
Examples 3-5 Other catalysts were prepared analogously to Example 1. Their ligands~~~the polymeri~ation conditions and the properties of the polarizing films ob~ained are shown in the following table.
Le A 26 406 - 15 -- ~ . :
:, : ~ -: - . , Z~305916t7 a~
.C ~~
,, ~r O O O
'H O ~ t.) P E-l o O S
o ~ ~ I ~r1 u~
a _, O
O
O O O O .
~ 3'~ a ~ . ~4 O O O
u~ ., ., ., ~
~ P~ v ~ u a ,~
~U C~ Z ~ Z _ Z _, a ..
G
~ ,~ Il O
~ Z
Le A 26 406 - 16 -.
t~ Table: Examples 3-5, Production and propertie~ of polarizing films - ~, r ,le1st absul~Lion St~etch ratio Qe 2 10 t;~ max P ~ 9596 P~
,p No. ~ of the in the wav~ ; in ~he wave reactn. soln. length rar~ge len~th range % ~n mn %
. - , 3 602 732 440-750 19.0 350-700 99.7 . .
: : 4 625 746 500-800 19.9 350-700 99.8 i~'3 637 7~ 450-75~ 25.4 400-700 99.8 .- -... --- : .
- - . . .
,. ~
.
.
= .
~, ~ .
Claims (9)
1. Highly effective polarizers in the form of stretched films, made from polymer products containing polyacetylene, whose matrix is a copolymer in which 70 to 90% of all comonomer units are vinyl alcohol units, the said polarizers having a maximum degree of polarization P of at least 95% and a dichroic ratio Q E, where Q E =
quotient of the extinction in the blocking position to the extinction in the transmitting position = 10 or more over almost the whole wavelength range of visible light from 400 to 800 nm.
quotient of the extinction in the blocking position to the extinction in the transmitting position = 10 or more over almost the whole wavelength range of visible light from 400 to 800 nm.
2. Polarizers according to Claim 1, with a stretch ratio .epsilon. of more than 300%; preferably at least 500%, particularly preferably at least 600%.
3. Polarizers according to Claim 1 with a maximum degree of polarization P of at least 98%, preferably at least 99% and a maximum Q E value of 15 and above, preferably 20 and above.
4. Highly effective polarizers which can be produced by polymerization of acetylene at 20-120°C during a period of 5-1000 sec. in the solution of a copolymer in which 70 to 90% of all comonomer units are vinyl alcohol units, in the presence of a nickel catalyst which is obtained by reacting a nickel (0) compound or a compound which can be converted in situ into a nickel (0) compound, with phosphorus compounds of the formulae and in which R1, R2 and R3 independently of each other denote C1-C8-alkyl, phenyl or benzyl, R4 represents hydrogen, C1-C8-alkyl or phenyl and R5, R6 and R7 independently of each other denote C1-C8-alkyl or phenyl, and R7 may additionally denote hydrogen or acyl, or in the presence of nickel catalysts which can be produced by reacting a nickel (0) compound or a compound which can be converted in situ into a nickel (0) compound, with an adduct or a mixture of p-benzoquinone and a phosphine of the formula in which R5 and R6 have the given meaning, and with a compound of the formula (I), by processing the polymer into films and by stretching the said films.
5. Polarizers according to Claim 4, characterized in that polymarization is carried out in the presence of a nickel catalyst which is obtained by reacting a nickel (0) compound with phosphorus compounds of the formulae and , in which R1, R2, R3 and R7 have the meaning given in Claim 4, or in the presence of nickel catalysts which can be prepared by reacting a nickel (0) compound or a compound which can be converted in situ into a nickel (0) compound, with an adduct or mixture of p-benzoquinone and triphenylphosphine and with a compound of the formula (IV).
6. Polarizers according to Claim 4, which have a stretch ratio 6 of more than 300%, preferably at least 500%, particularly preferably at least 600%.
7. Polarizers according to Claim 4, which can be produced at a concentration of 10-1 to 10-5, preferably 10-2 to 10-4 mol of Ni catalyst per litre of polymerization mixture.
8. Polarizers according to Claim 4, for which a duration of 5-300 seconds, preferably of 5-200 seconds is used for the polymerization.
9. Polarizers according to Claim 4, characterized by adhesive layers and outer layers applied to one or both sides.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3842967 | 1988-12-21 | ||
DEP3842967.5 | 1988-12-21 | ||
DEP3905027.0 | 1989-02-18 | ||
DE19893905027 DE3905027A1 (en) | 1988-12-21 | 1989-02-18 | HIGHLY EFFECTIVE POLARIZERS |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2005967A1 CA2005967A1 (en) | 1990-06-21 |
CA2005967C true CA2005967C (en) | 1999-05-04 |
Family
ID=25875398
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2005967 Expired - Fee Related CA2005967C (en) | 1988-12-21 | 1989-12-19 | Highly effective polarizers |
Country Status (6)
Country | Link |
---|---|
US (1) | US5051286A (en) |
EP (1) | EP0374627B1 (en) |
JP (1) | JP2865140B2 (en) |
CA (1) | CA2005967C (en) |
DE (2) | DE3905027A1 (en) |
FI (1) | FI95969C (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3905519A1 (en) * | 1989-02-23 | 1990-08-30 | Bayer Ag | HIGHLY EFFECTIVE POLARIZERS |
DE4211779A1 (en) * | 1992-04-08 | 1993-10-14 | Agfa Gevaert Ag | Manufacture of polarizing films |
EP0962807B1 (en) | 1993-12-21 | 2008-12-03 | Minnesota Mining And Manufacturing Company | Multilayered optical film |
US6096375A (en) * | 1993-12-21 | 2000-08-01 | 3M Innovative Properties Company | Optical polarizer |
DE4430096A1 (en) * | 1994-08-25 | 1996-02-29 | Agfa Gevaert Ag | Thermostable polarizers |
DE4434964A1 (en) * | 1994-09-30 | 1996-04-04 | Agfa Gevaert Ag | Polarizing film |
DE19503282A1 (en) * | 1995-02-02 | 1996-08-08 | Bayer Ag | Use of matrix polyacetylenes for non-linear optical elements |
DE19606386A1 (en) * | 1996-02-21 | 1997-08-28 | Bayer Ag | Composite material |
DE69835729T2 (en) * | 1997-03-19 | 2007-09-20 | KURARAY CO., LTD, Kurashiki | POLARIZATION FILM |
US7573637B2 (en) * | 2004-08-03 | 2009-08-11 | Seiko Epson Corporation | Intrinsic polarizer and method of manufacturing an intrinsic polarizer |
US20090163686A1 (en) * | 2007-12-20 | 2009-06-25 | 3M Innovative Properties Company | Method of making an intrinsic polarizer |
NL2029163B1 (en) | 2021-09-09 | 2023-03-23 | Lankhorst Touwfab Bv | Polarizing light filter |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS572001A (en) * | 1980-06-04 | 1982-01-07 | Toyobo Co Ltd | Manufacture of polarizing film |
JPS5977401A (en) * | 1982-09-22 | 1984-05-02 | Nitto Electric Ind Co Ltd | Polarizing plate |
DE3403493C2 (en) * | 1984-02-02 | 1994-02-03 | Bayer Ag | Process for the polymerization of acetylene |
DE3526234A1 (en) * | 1985-07-23 | 1987-01-29 | Bayer Ag | METHOD FOR THE POLYMERIZATION OF ACETYLENE IN THE PRESENCE OF POLYMERS AND POLYMER PRODUCTS CONTAINING POLYACETYLENE |
DE3615765A1 (en) * | 1986-05-10 | 1987-11-12 | Bayer Ag | POLYACETYLENE-BASED POLARISATORS AND THEIR PRODUCTION |
DE3617502A1 (en) * | 1986-05-24 | 1987-11-26 | Basf Ag | Transparent, electrically conductive multilayer films |
-
1989
- 1989-02-18 DE DE19893905027 patent/DE3905027A1/en not_active Withdrawn
- 1989-12-06 US US07/446,944 patent/US5051286A/en not_active Expired - Lifetime
- 1989-12-08 EP EP19890122659 patent/EP0374627B1/en not_active Expired - Lifetime
- 1989-12-08 DE DE58909062T patent/DE58909062D1/en not_active Expired - Fee Related
- 1989-12-19 FI FI896091A patent/FI95969C/en not_active IP Right Cessation
- 1989-12-19 CA CA 2005967 patent/CA2005967C/en not_active Expired - Fee Related
- 1989-12-20 JP JP33096089A patent/JP2865140B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE58909062D1 (en) | 1995-04-06 |
JP2865140B2 (en) | 1999-03-08 |
EP0374627B1 (en) | 1995-03-01 |
DE3905027A1 (en) | 1990-06-28 |
CA2005967A1 (en) | 1990-06-21 |
FI896091A0 (en) | 1989-12-19 |
FI95969B (en) | 1995-12-29 |
US5051286A (en) | 1991-09-24 |
EP0374627A3 (en) | 1991-09-04 |
JPH02282201A (en) | 1990-11-19 |
FI95969C (en) | 1996-04-10 |
EP0374627A2 (en) | 1990-06-27 |
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